Process for the preparation of dyeings and prints which are fast to wet processing



United States Patent 3,223,470 PRUCESS FOR THE PREPARATION OF DYEINGS AND PRINTS WEHCH ARE FAST TO WET PRGC- E$SING Hermann Boedeker, Frankfurt am Main, Gerhard Langbein, Hofheim, Taunus, Karl Summer, Konigstein, Taunus, Hans Zimmermann, Hofheim, Taunus, and Klaus Berner, Frankfurt am Main, Germany, assignors to Farbwerke Hoechst Aktiengesellschaft vormals Meister Lucius & Briining, Frankfurt am Main, Germany, a corporation of Germany No Drawing. Filed May 1, 1962, Ser. No. 191,439 Claims priority, application Germany, May 6, 1961, F 33,866 5 Claims. (Cl. 8-89) The present invention provides a process for the preparation of dyeings and prints which are fast to wet processmg.

We have found that fast dyeings and prints can be produced on various fibrous materials, for example such as natural or regenerated cellulose fibers, wool, silk or polyamide fibers, by applying to the fibrous material water soluble dyestufis which contain the grouping and at least one of the groupings in which X represents a halogen atom and Y represents the radical of a polybasic acid, and by fixing the dyestuffs at normal or raised temperature in the presence of agents giving an alkaline reaction. As polybasic acids the radical of which is represented by Y there are used, for example, sulfuric acid, phosphoric acid, boric acid, benzeneor naphthalene-polysulfonic acids, or benzeneor naphthalene-polycarboxylic acids. The fixation of the dyestuffs can be carried out within a large temperature range, suitably between about 18 C. and about 130 C.

As dyestuffs of the type mentioned which may contain groups imparting solubility in water such as, for example, the sulfonic acid-, carboxylic acidor sulfonic acid-amide group, various dyestuifs may be used, for example azodyestuffs and the complex metal compounds thereof such as the copper, cobalt, and chromium compounds, furthermore anthraquinone dyestufis, phthalocyanine dyestuffs as well as the complex metal compounds thereof such as the copper and nickel compounds, dioxazine, azine, triphenylmethane and stilbene dyestuifs. They may be prepared for example in such a manner that 1 mol of cyanuric chloride is first reacted with 1 mol of an aminoaryl-fl-hydroxyethylsulfone or the sulfuric acid ester thereof, an aminoaryl-vinylsulfone or an aminoaryl-B- chloro-ethylsulfone, and then with 1 mol of a dyestuff containing an amino group which can be acylated. When using an aminoaryl-fi-hydroxyethylsulfone, the dyestuff obtained must subsequently be converted into the monoester of a polybasic acid. It azo-dyestuffs are used, it is also possible to react the first-formed condensation product with 1 mol of a diazo component or of a coupling component containing an amino group which can be acylated and which is not necessary for the diazotization or.coupling. The corresponding dyestuffs are subsequently prepared by reaction with a coupling component or with a diazo component respectively.

The condensation of the components with cyanuric chloride may also be conducted in a different order. It is equally possible to condense 1 mol of cyanuric chloride, dichloropyrimidine or trichloropyrimidine with, for example, 2 mols of a coupling component containing an amino group which can be acylated and then to couple the condensation products With diazotized aminoaryl-B- hydroxyethylsulfonic acid esters, aminoaryl 5 chloroethylsulfones or aminoaryl-vinylsulfones, or to condense cyanuric chloride with amine dyestufis already containing a 8 hydroxyethylsulfonic acid ester-, 8 chloro ethylsulfoneor vinylsulfone-group. The dyestufis may also be metallized subsequently. With the above-mentioned manufacturing processes, the possibilities are not ex hausted.

The novel process can be conducted, for example, according to the direct dyeing method by dyeing the dyestulf With the addition of alkaline agents, if desired in the presence of electrolytes, in a long liquor and, if necessary, fixing by gradually raising the temperature of the bath. If there exists no or no pronounced afiiinity to the fiber, it is advantageous to workwith the aid of a continuous dyeing process, for example by padding cellulose fiber with a solution of the dyestuif and then, suitably after intermediate drying, passing this cellulose fiber through a bath containing an alkaline agent or an agent yielding alkali such as, for example, sodium hydroxide, sodium carbonate, sodium bicarbonate, trisodium phosphate, the sodium salt of trichloroacetic acid or the corresponding potassium or alkaline earth metal compounds, whereupon the dyestufiafter having once more been dried is fixed by steaming or dry heating. The alkaline agent may also be added to the padding liquor, which saves one process step. It is also possible to pad the fiber first with the solution of an alkaline agent and then with the dyestuif solution and to fix it in the manner described above.

If the impregnation of the fibrous material is carried out, for example, in the presence of an alkali hydroxide, fixation of the dyestuifs can also be conducted in the cold or at a moderately elevated temperature according to the so-called pad batch process by allowing the impregnated fibrous material to stand for several hours.

For printing it is advantageous to apply the dyestuil to the fiber together with a thickening agent, for example, sodium alginate, methyl cellulose, starch ether or an emulsion thickening and one of the alkaline agent-s described above, if desired with the addition of the usual printing auxiliaries as for example urea or a dispersing agent, to dry the material and to subject it to a heat reatment, preferably in the presence of steam.

It is also possible to apply a printing paste containing no alkali but only dyestuif, thickening agent and printing auxiliaries to a material prepared with alkali. After drying these prints, fixation is carried out by the usual heat treatment, for example in a steamer.

Furthermore, such a printing paste containing no alkali may be printed onto a material which has not been prepared with alkali. After drying, the printed material is passed through a padding liquor containing alkali and, if desired electrolytes such as, for example, sodium chloride, or it is padded with a correspondingly thickened solution. The fixation of the dyestuifs is then carried out by an immediately following heat treatment of the material, for example in a rapid ager, in an electro fixer, in a tenter frame or in the wet state at raised temperature, for example by a short passage through a salt bath. Furthermore, fixation may be attained in such a manner that the printed material is not passed through a cold padding liquor but through a hot padding liquor, for example at temperatures between 50 and C., whereby the padding liquor may contain alkali and electrolytes.

The dyeings and prints obtained by the process of the present invention possess very good fastness properties,

3 4 particularly a good fastness to wet processing and to light. bath and the dyeing is continued for hours. The mate- The following examples serve to illustrate the invention rial is then rinsed and soaped at boiling temperature. The but they are not intended to limit it thereto, the parts orange dyeing obtained possesses a good fastness to wet being by weight unless otherwise stated and the relationprocessing and to light. ship of parts by Weight to parts by volume being the same 5 Example 2 as that of kilogram to the liter.

20 parts of the dyestuif obtainable in an analogous Example 1 manner as described in Example 1 with the use of l-amino- 18.4 parts of cyanuric chloride are dissolved in 100 8-hydroXynaphtl1alene-3,6-disulfonic acid, and which dyeparts of acetone and the clear solution is poured, While 10 stutf corresponds in the form of its free acid to the fOllOW- stirring, onto 400 parts of crushed ice. At that tempering formula ('31 PIT N HOsSOCH2CHr-SO NEE-C JJ-NH OH 11038 HOaS- SOaH ature ranging from 0 to C. a solution of 28.1 parts are dissolved in water. parts by volume of sodium hyof 1aminobenzene-3-,3-hydroxyethylsulfone-sulfuric acid droxide solution of 38 B. are added and the whole is ester and 19 parts of crystallized sodium acetate in 300 madeup to 1000 parts by volume by the addition of water. parts of Water and a solution of 14 parts of crystallized In the dyeing bath so obtained cotton fabric is impregsodium acetate in 100 parts of Water are introduced simult d at 20 C, The fabric is then squeezed off to an taneously While vigorously stirring. Stirring is continued i rea f weight of about 80%, rolled on a roller, for 1 to 2 hours until a withdrawn sample contains no Wrapped in a foil and left on the roller while turning the more diazotizable material. Subsequently a neutral solul t f b t ;16 hour at a temperature between 18 tion of Parts of Y Y P and 25 C. The dyeing is then acidified, rinsed in boiling fonic acid and 5.5 parts of sodium carbonate free from water and dried, A clear red dyeing possessing a good waterin '250 parts of water is introduced and 18 parts of fastness to wet processing and to light is obtained.

crystallized sodium acetate are added. The temperature is gradually raised to room temperature and the mixture Example 3 is stirred for about 20 hours. After the addition of a further 40 parts of crystallized sodium acetate, coupling to 10 parts f linen f bri are dyed on a jigger for .30 form the monoazo dyestuff is carried out at room temperminutes at in 500 Pal-ts by volume f a liquor a u e w the dlaZOnlum flompolmd Prepared 1n the usutll 40 taining 25 parts of sodium sulfate and 5 parts of a dyestufl? manner from Parts of l'ammobenzenez'slflfomc having a content of pure substance of and correacid. After stirring for several hours the separation of sponding in the f f i f i to the fgllowing the dyestuif is completed by the addition of sodium chloformula r r HOaSO-CHrCHa-SO NHC C-NH 031 HOaS -N=N- -o1 H0:s SO3H COOH ride; it is suction filtered off and dried at 50 C. The dyestulf obtained in the form of a dark powder dissolves in water to give an orange solution. In the form of its free acid it corresponds to the following formula Subsequently 10 parts of sodium carbonate free from water are added to the dye bath and dyeing is continued for 1 hour. After acidifying, rinsing and soaping at boiling 100 parts of cotton yarn are dyed for 30 minutes at 40 C. temperature, a clear red dyeing possessing very good fastin 3000 parts by volume of a bath containing in dissolved ness properties is obtained.

form 5 parts of the dyestufl described above having a content of pure substance of 50% and 150 parts of sodium sulfate free from Water. Subsequently 45 parts of 100 parts of cotton fabric are dyed for 30 minutes at crystallized trisodium phosphate are added to the dyeing 60 C. in 3000 parts by volume of a liquor containing in Example 4 dissolved form 5 parts of dyestulf obtainable in a similar 4 N-sodium acetate solution and the solution is stirred manner as described in Example 1, Which dystutf correuntil the coupling is complete. The solution is heated to sponds to the following formula 40 C. and the dyestuff is salted out by the addition of (I31 f \N NH-C d-NH OH H035 HOaS SO3H and 150 parts of sodium sulfate free from water. Subse- 150 parts of potassium chloride, suction filtered off and quenfly 60 Parts of Sodium j from Water are dried. The dyestutf obtained in the form of a dark blue added to the dye bath and dyeing is continued for 1 hour. d l f t H d olufo After rinsing and soaping at boiling temperature, a clear pow er Iss0 m waer o g 1ve a ye e s 1 n red dyeing Possessing a Very good fasmess to washing and 2 and corresponds in the form of 1ts free acid to the followto light is obtained. ing formula ('31 i NHC C-NH S0aH OH I Hots OCH:C H:-S o N=N NHC O-GHz-C Hz-S 02H HOsS Example 5 Linen fabric is padded with a solution containing 30 grams/liter of the above-mentioned dyestufi having a content of pure substance of 50%. After squeezing off, an intermediate drying follows. Then the mixture is sloppadded with a solution containing 200 grams/liter of sodium sulfate free from Water and grams/liter of sodium hydroxide solution of 38 B6. The material is squeezed off and steamed for 20 to seconds at -100 to 105 C. The ruby red dyeing possesses very good fastness properties.

l8.8 parts of l,4-diaminobenzene-2-sulfonic acid are dissolved in 400 parts of Water with about 7 parts of sodium carbonate free from Water and clarified. 20 parts of 40 crystallized sodium acetate are then added and at 0 to +5 C. a solution of 418.4 parts of cyanuric chloride in 100 parts of acetone is added dropwise while stirring well, whereby a suspension forms. The pH-value of 5 is maintained by adding dropwise a 4 N-sodium acetate solution and the mixture is stirred for 2 hours at 0 to +5 C. After separation of the ice bath, 20 parts of crystallized sodium acetate are introduced and a suspension of 28.1 Example 6 parts of l-aminobenzene-4- 8-hydroxyethylsulfone-sulfuric Mercerized cotton fabric is padded with a solution conacid ester in 300 parts of water is poured in at room temtaining 30 grams/liter of the dyestutf having a content of perature. The pH-value of 5 is again maintained by addpure substance of 50% prepared in a similar manner as mg dropwise a 4 N-sodium acetate solution and the mixdescribed in Example 5 and corresponding to the folture is stirred for about 20 hours at room temperature, lowing formula e 3 NH-C (il-NH N=N- HO3SO-CHz-CH:SO:- 303E SOaH- SO|H whereby all its constituents are dissolved. Subsequently After squeezing off to an increase of weight of 80%, the the solution obtained is cooled to 0 to +3 C., 30 parts material is subjected to an intermediate drying. It is then of concentrated hydrochloric acid are added, and by addtreated for 40 minutes at C. on the jigger with a soluing dropwise about 20 parts by volume of 5 N-sodium nition containing 300 grams/liter of sodium chloride and trite solution it is diazotized. The acid is then saturated 3O grams/liter of crystallized trisodium phosphate. After with 100 parts by volume of 4 N-sodium acetate solution, 70 acidifying, rinsing and soaping at boiling temperature, a

a clarified solution and of 37.5 parts of 2-(B-sulfopropiclear bluish red dyeing possessing very good fastness onyl)-amino-8-hydroxynaphthalene-6-sulfonic acid and 7 properties is obtained. parts of sodium carbonate free from water in 250 parts A dyeing possessing a similar tint and similar fastness of water is added dropwise. The pH-value of 4.5 is mainproperties is Obtained y using the y fi which contained by adding dropwise about 50 parts by volume of tains as coupling component the 1-benzoylamino-8-hy- 7 8 droxynaphthalene-4,6-disulfonic acid instead of the cor-. The secondary condensation product which has been responding 3,6-disulfonic acid. precipitated by the addition of 80 parts of potassium chlo- E I 7 ride is separated and dissolved in 600 parts of water. 6 After the addition of 25 parts of potassium acetate free Staple fiber fabric is padded with a solution containing from water, 20 parts of the diazo-oxide of 2-amino- 30 grams/liter of the following dyestutf pheno1-4-sulfonic acid are introduced and the mixture is I NH JJ-NH OH HOsS I Ho;so-on,cn,-s0 N: G

SOsH S OzH having a content of pure substance of about 60%, 100 stirred at room temperature until the coupling is comgrarns/liter of urea, 10 grams/liter of the sodium salt of plete. By the addition of potassium chloride the dyestutf metanitrobenzene-sulfonic acid and grams/liter of sois salted out and suction filtered oif. It is then dissolved dium bicarbonate. The material is squeezed off and dried. in 1500 parts of water and, after the addition of 25 parts It is then steamed for 5 minutes at 100 to 105 C., rinsed of crystallized copper sulfate and 55 parts of crystaland soaped at boiling temperature. A clear red dyeing lized sodium acetate, heated for about 3 hours at 80 C. possessing a very good fastnessto wet processing and a while stirring, After cooling, the complex copper dyegood fastness to light is obtained. stuff is precipitated with sodium chloride, suction filtered E l 8 oif and dried. It is a dark powder which dissolves in xamp e Water to give a ruby red solution. In the form of its free 28.2 parts of 1-aminobenzene-4-fl-hydroxyethylsu1foneacid the dyestuff corresponds to the following formula ([31 0 C o l \N I 5' Nn-h e-NH -NN HOzSO-CHz-CHr-SO S 03H SOtH sulfuric acid ester are neutralized at 10 to 15 C. while 30 parts of this dyestuff having a content of pure substirring in 150 parts of water by the addition of little more stance of about are dissolved with 50 parts of urea in than 10 parts of potassium bicarbonate. The solution is 200 parts of hot water. After cooling, 400 parts of a then heated in 50 C. and clarified. 150 parts of ice are thickening consisting of 40 parts of sodium aliginate and added to the filtrate and 18.4 parts of cyanuric chloride 960 parts of Water and 20 parts of sodium bicarbonate are are introduced. The mixture is then stirred for several 50 added while stirring. The paste is then made up to 1000 hours at 0 to +5 C. until a sample which has been adparts by adding water,

mixed with hydrochloric acid and sodium nitrite no longer A cotton fabric is printed with the paste obtained; after shows a coupling reaction with 2-naphthol-3,6-disulfonic drying it is steamed for 5 minutes at 101 to 103 (3., acid. By adding dropwise about 40 par s o a po i m rinsed with cold water, then with hot water, soaped at bicarbonate solution of 25 strength, the neutral point boiling temperature, rinsed again and dried. A ruby is adjusted again. Then 25 parts of Z-amino-S-hydroxyprint possessing a good fastness to wet processing and to naphthalene-6-sulfonic acid of 96% strength are added, light is obtained.

the mixture is once more neutralized by adding potassium With the complex cobalt dyestutf obtained by treating bicarbonate and heated to 40 to 45 C. The mixture is the starting dyestuif with an agent yielding cobalt, a curstirred for several hours at that temperature and the pH rant print is obtained. value is maintained at about 4 by slowly adding dropwise a potassium bicarbonate solution of 25% strength until it Example 9 is no longer possible to prove diazotizable content. At the end of the reaction, the neutral point is adjusted again. The dyestufi having the following formula II I 9 10 which is obtainable by reacting the condensation product printed with a printing paste having the composition deof 1-amino-4-bromoanthraquinone-Z-sulfonic acid and 1 scribed in Example 11. Fixation is carried out by steammol of 1,4-diaminobenzene-Z-sulfonic acid with the coning for minutes at 101 to 103 C. in a usual Mather densation product of cyanuric chloride and 1 mol of 1- Platt. After rinsing and soaping a fast brilliant red print aminobenzene-3-;8-hydroxyethylsulfone-sulfuric acid ester, 5 is obtained. is printed on viscose rayon fabric in the same manner as Example 13 described 1n Example 7. A greenish blue pri P 40 parts of the dyestufif described in Example 7 are mg Very good fasmess PTOPertleS Obtameddissolved with 50 parts of urea in 250 parts of hot wa- Exzrmple 10 ter. This solution is introduced, while stirring, into 400 30 parts of a dyestufl which is obtainable by reacting 10 Parts of a neutral Sodium alghlate thickening of 4% copper phthalocyanine-tetrasulfochloride with the conden- Strength After Cooling the Printing color, Parts of Sation Product of cyanuric hl 'd 1 l f li b dium acetate are added; subsequently the solution obtained zene-4- 3-hydroxyethylsulfone-sulfuric acid ester and 1 mol is m del p t I OQ PFEt b iggya q th g p pgof l,4-diaminobenzene-2-sulfonic acid, and which corre- With this printing paste, silk is printed. Fixation is carsponds to the following formula 15 ried out in the usual manner by steaming. Brilliant N/ Cl are dissolved with 50 parts of urea in 200 parts of hot wared prints possessing agood fastness to wet processing ter. 400 parts of an aqueous starch ether thickening of are obtained. 10% strength and 40 parts of trisodium phosphate are Examl 14 then added. The paste obtained is made up to 1000 parts 40 parts f h d t fl d s rib d in Example 7 are y adding water and thickening After printing, fixing dissolved with 50 parts of urea in 250 parts of hot water. and fimshihg 1n the manner descflbed 111 Example 8, 0 This solution is introduced while stirring into 400 parts quoise blue P s possessing a good fastness to Washing of a neutral sodium alginate thickening dr 4% strength; are obtained on cellulose fabrics or on fabrics of regener- Subsequently 100 Parts f a Solution of the Sodium Salt ated Cellulose of trichloroacetic acid in water (1:1) are added and the Example 11 solution obtained is made up to 1000 parts by adding 40 parts of the dyestuff having the following formula 35 water and thickening. With this printing color, brilliant (:1 on NH (Jo-Q N N 1 1 NHi JNH --N N nmso-om-orwso sod1 Hots SOaH are dissolved by heating with 50 parts of urea in 250 red prints possessing a good fastness to wet processing parts of water. This solution is introduced while stirring are obtained on Wool after fixing by steaming. into 400 parts of a neutral sodium alginate solution of 4% strength and the solution so obtained is then made Example 15 up to 1000 parts by adding water and thickening. The printing color obtained is printed on cellulose fabric. After printing and drying, the material is passed through a cold padding liquor containing per liter of liquor 20 parts of sodium hydroxide solution of 38 B., 150 parts of sodium carbonate, 50 parts of potassium carbonate and 100 parts of sodium chloride. Subsequently the material is steamed for 30 seconds at 118 to 120 C. on a rapid ager. After finishing in the usual manner, a brilliant red print is obtained.

Fixation of the printed material may also be carried 100 parts of a polyarnide'fabric are treated for about 10 minutes at 40 C. in 3000 parts by volume of a liquor containing in dissolved form 2 parts of the dyestuff described in Example 7 and 6 parts of crystallized trisodium phosphate. The dye bath is then acidified by adding formic acid, acetic acid or sulfuric acid and the material is dyed for 1 hour at boiling temperature. A scarlet dyeing possessing a high brilliancy and very good fastness properties is obtained.

out by passing the material through a padding liquor Examp [e Z of the ahoflejmentioned cqmposltwq t about 9 100 parts of combed Wool material are treated for about h then Tlhslng e A slmllar result 15 9 10 minutes at 40 C. in 1000 parts by volume of a liquor tamed as by proceeding 1n the manner described earlier containing in dissolved form 7 pants of acetic acid Qf above. 50% strength and 10 parts of sodium sulfate free from Example 12 water. After the addition of a concentrated aqueous Cotton is padded with a liquor containing 10 cc./l. of solution which contains 2 parts of the dyestutf corressodium hydroxide solution of 38 B. and, after drying, pending to the following formula $1 0 OH 1103s t t NH-C C-NH -N=NO01 1 1 having a content of pure substance of 50% and which, after the addition of 2 parts of crystallized trisodium phosphate has been left for 10 minutes at 40 C. in the alkaline range, the bath is heated to boiling temperature and the 12 solved disodium phosphate, and rinsed again. A scarlet dyeing possessing very good fastness properties is obtained.

Dyeings and prints possessing good fastness properties material is dyed for 1 hour at this temperature. It is 5 are obtained in a similar manner as described in the then rinsed and treated for 30 minutes at 80 C. in 1500 previous examples by using the dyestuffs listed in the parts by volume of a new bath containing 3 parts of dis following table.

Composition Tint El bluish red. N N HOaSO-CHr-CHrSOz- NHi l-NH OH CHAO I l HOHS -sO;H SO CH=CH ('31 D0. N ITT OCH: OH NH-l C NH OH OCH:

N N=N N=N H035 -SO3H H033 SO3H (HO)1OPOCHg-CHTSOI SOr-CHr-CH;-OPO(OH);

(31 yellowish red. OH /C\ OH N 1 N=N N11ii C-NH -N=N HO:SO-CHr-CHr-SO HOaS SO:H SOTCHfiCHQ OSOJH 1'3! bluish red. N N t NH- C-NH S0311 HOISO-CH1CHTSO N:

H0=s -SO5H i1 greenish yellow.

N N OH g l (5 $0211 NH- /CNH- -N=N-O= HO;SO-CH;CHS O S OaH C N/ SOaH COOH (31 yellow. N N a t 0H HOaSO-CHrCHg-S Oz NH- -NH & =CN=N SO2CHzCHrOSOaH Composition Tint O NH; blue. H l

:1 ll NH /(3\ i i NHC ONH -soicnicni-ososrr N ('31 C'l blue violet.

SOaH 0 N o NHC/ C-NE- x -s0,-c111 1% N N 110 so on: on so NH ii ('1 NH (12H2 3 2- r 0/ N/ \O/ OSOH I 11035 I N c1 or We claim:

1. In a process for dyeing fibrous articles of a material selected from the group consisting of natural cellulose, regenerated cellulose, wool, silk and polyamides, the improvement which comprises applying to said fibrous articles a water-soluble organic dyestufi selected from the group consisting of azo-, complex metal azo-, phthalocyanine, complex metal phthalocyanine, anthraquinone, and d-ioxazine dyestuffs, said dyestuffs containing 1 to 4 radicals selected from the group consisting of and and 1 to 4 substituents selected from the group consisting Of -SO2-CH=CH2, and

-SO2CH 2 References Cited by the Examiner UNITED STATES PATENTS 3,046,075 7/1962 Kantner et al 81.2

FOREIGN PATENTS 1,252,324 12/1960 France.

111,302 12/1961 Pakistan.

NORMAN G. TORCHIN, Primary Examiner.

50 ABRAHAM H. WINKELSTEIN, Examiner. 

1. IN A PROCESS FOR DYEING FIBROUS ARTICLES OF A MATERIAL SELECTED FROM THE GROUP CONSISTING OF NATURAL CELLULOSE, REGENERATED CELLULOSE, WOOL, SILK AND POLYAMIDES, THE IMPROVEMENT WHICH COMPRISES APPLYING TO SAID FIBROUS ARTICLES A WATER-SOLUBLE ORGANIC DYESTUFF SELECTED FROM THE GROUP CONSISTING OF AZO-, COMPLEX METAL AZO-, PHTHALOCYANINE, COMPLEX METAL PHTHALOCYANINE, ANTHRAQUINONE, AND DIOXAZINE DYESTUFFS, SAID DYESTUFFS CONTAINING 1 TO 4 RADICALS SELECTED FROM THE GROUP CONSISTING OF 